Alkene radical ions constitute an integral and unique class of reactive intermediates for the synthesis of valuable compounds, because they have both unpaired spins and charge. However, relatively few synthetic applications of alkene radical anions have emerged, due to a dearth of generally applicable and mild radical anion generation approaches. Precise control over the chemo- and stereoselectivity in alkene radical anion-mediated processes represents another long-standing challenge due their high reactivity. To overcome these issues, here, we develop a new redox-neutral strategy that seamlessly merges photoredox and copper catalysis to enable the controlled generation of alkene radical anions and their orthogonal enantioselective diversification via distonic-like species. This new strategy enables highly regio-, chemo- and enantioselective hydrocyanation, deuterocyanation, and cyanocarboxylation of alkenes without stoichiometric reductants or oxidants under visible light irradiation. This work demonstrates the power of photochemistry in expanding new chemical space and overcoming persistent challenges in radical anion chemistry.